Molecular approaches to smart materials via interface recognition and conformationally switchable cavitands

In this thesis the molecular level design of functional materials and systems is reported. In the first part, tetraphosphonate cavitand (Tiiii) recognition properties towards amino acids are studied both in the solid state, through single crystal X-ray diffraction, and in solution, via NMR and ITC experiments. The complexation ability of these supramolecular receptors is then applied to the detection of biologically remarkable N-methylated amino acids and peptides using complex dynamic emulsions-based sensing platforms. In the second part, a general supramolecular approach for surface decoration with single-molecule magnets (SMMs) is presented. The self-assembly of SMMs is achieved through the formation of a multiple hydrogen bonds architecture (UPy-NaPy complexation). Finally we explore the possibility to impart auxetic behavior to polymeric material through the introduction of conformationally switchable monomers, namely tetraquinoxaline cavitands (QxCav). Their interconversion from a closed vase conformation to an extended kite form is studied first in solution, then in polymeric matrixes via pH and tensile stimuli by UV-Vis spectroscopy.

Multiwavelength study of quiescent states of MrK 421 with unprecedented hard x-Ray coverage provided by NuStar in 2013

We present coordinated multiwavelength observations of the bright, nearby BL Lacertae object Mrk 421 taken in 2013 January–March, involving GASP-WEBT, Swift, NuSTAR, Fermi-LAT, MAGIC, VERITAS, and other collaborations and instruments, providing data from radio to very high energy (VHE) γ-ray bands. NuSTAR yielded previously unattainable sensitivity in the 3–79 keV range, revealing that the spectrum softens when the source is dimmer until the X-ray spectral shape saturates into a steep G » 3 power law, with no evidence for an exponential cutoff or additional hard components up "aprox" 80keV. For the first time, we observed both the synchrotron and the inverse-Compton peaks of the spectral energy distribution (SED) simultaneously shifted to frequencies below the typical quiescent state by an order of magnitude. The fractional variability as a function of photon energy shows a double-bump structure that relates to the two bumps of the broadband SED. In each bump, the variability increases with energy, which, in the framework of the synchrotron self-Compton model, implies that the electrons with higher energies are more variable. The measured multi band variability, the significant X-ray-toVHE correlation down to some of the lowest fluxes ever observed in both bands, the lack of correlation between optical/UV and X-ray flux, the low degree of polarization and its significant (random) variations, the short estimated electron cooling time, and the significantly longer variability timescale observed in the NuSTAR light curves point toward in situ electron acceleration and suggest that there are multiple compact regions contributing to the broadband emission of Mrk 421 during low-activity states.

Multiwavelength study of star-forming galaxies in the local Universe

We have studied in detail the properties of local active star-forming galaxies from the UCM survey, and in particular their star-formation histories. We have quantified the relative importance of the current episode of star formation in comparison to the underlying older stellar populations. We have also determined the total stellar mass function and burst mass function for the UCM sample using the M/L calculated for each galaxy. Integrating this mass function we obtained the contribution of the star-forming galaxies to the total stellar mass density of the local Universe.

Switchable surfactant-assisted carbon nanotube coatings: innovation through pH shift

The inner surface of fused-silica capillaries has been coated with a dense/homogeneous coating of commercial multi-wall carbon nanotubes (MWCNTs) using a stable ink as deposit precursor. Solubilization of the MWCNTs was achieved in water/ethanol/dimethylformamide by the action of a surfactant, which can switch between a neutral or an ionic form depending on the pH of the medium, which thus becomes the driving force for the entire deposition process. Careful control of the experimental conditions has allowed us to selectively deposit CNTs on the inner surface of insulating silica capillaries by a simple, reproducible, and easily adaptable method.

Multiwavelength study of the fast rotating supergiant high-mass X-ray binary IGR J16465−4507

Context. Since its launch, the X-ray and γ-ray observatory INTEGRAL satellite has revealed a new class of high-mass X-ray binaries (HMXB) displaying fast flares and hosting supergiant companion stars. Optical and infrared (OIR) observations in a multi-wavelength context are essential to understand the nature and evolution of these newly discovered celestial objects. Aims. The goal of this multiwavelength study (from ultraviolet to infrared) is to characterise the properties of IGR J16465−4507, to confirm its HMXB nature and that it hosts a supergiant star. Methods. We analysed all OIR, photometric and spectroscopic observations taken on this source, carried out at ESO facilities. Results. Using spectroscopic data, we constrained the spectral type of the companion star between B0.5 and B1 Ib, settling the debate on the true nature of this source. We measured a high rotation velocity of v = 320 ± 8km s-1 from fitting absorption and emission lines in a stellar spectral model. We then built a spectral energy distribution from photometric observations to evaluate the origin of the different components radiating at each energy range. Conclusions. We finally show that, having accurately determined the spectral type of the early-B supergiant in IGR J16465−4507, we firmly support its classification as an intermediate supergiant fast X-ray transient (SFXT).

Peptide surfactants (Pepfactants) for switchable foams and emulsions

We have developed a series of sustainable peptide surfactants (Pepfactants) capable of stabilizing foams and emulsions in a stimuli-responsive manner, based on the reversible formation of a mechanically strong interfacial film. Under conditions where the interfacially adsorbed peptide forms a mechanically strong film state, foam or emulsion stabilization occurs as a direct result of the film strength. Under conditions where the interfacially adsorbed peptide forms a mobile detergent state, foam or emulsion stabilization is either reduced, or does not occur. Preformed foams or emulsions stabilized by Pepfactants undergo rapid phase coalescence when the film state is converted to the detergent state. Switching between film and detergent states is readily and reversibly achieved by a change in the bulk solution composition, such as a change in pH, or the addition or sequestering of metal ions. Copyright © 2007 Curtin University of Technology and John Wiley & Sons, Ltd.

Advanced UV inscribed fibre grating structures and applications in optical sensing and laser systems

This thesis presents detailed investigation of UV inscribed fibre grating based devices and novel developments in the applications of such devices in optical sensing and fibre laser systems. The major contribution of this PhD programme includes the systematic study on fabrication, spectral characteristics and applications of different types of UV written in-fibre gratings such as Type I and IA Fibre Bragg Gratings (FBGs), Chirped Fibre Bragg Gratings (CFBGs) and Tilted Fibre Gratings (TFGs) with small, large and 45º tilted structures inscribed in normal silica fibre. Three fabrication techniques including holographic, phase-mask and blank beam exposure scanning, which were employed to fabricate a range of gratings in standard single mode fibre, are fully discussed. The thesis reports the creation of smart structures with self-sensing capability by embedding FBG-array sensors in Al matrix composite. In another part of this study, we have demonstrated the particular significant improvements made in sensitising standard FBGs to the chemical surrounding medium by inducing microstructure to the grating by femtosecond (fs) patterning assisted chemical etching technique. Also, a major work is presented for the investigation on the structures, inscription methods and spectral Polarisation Dependent Loss (PDL) and thermal characteristics of different angle TFGs. Finally, a very novel application in realising stable single polarisation and multiwavelength switchable Erbium Doped Fibre Lasers (EDFLs) using intracavity polarisation selective filters based on TFG devices with tilted structures at small, large and exact 45° angles forms another important contribution of this thesis.

Single- and dual-wavelength switchable erbium-doped fiber ring laser based on intracavity polarization selective tilted fiber gratings

We propose and demonstrate a single- and dual-wavelength switchable erbium-doped fiber laser (EDFL) by utilizing intracavity polarization selective filters based on tilted fiber gratings (TFGs). In the cavity, one 45° TFG functions as an in-fiber polarizer and the other 77° TFG is used as a fiber polarization dependent loss (PDL) filter. The combined polarization effect from these two TFGs enables the laser to switch between the single- and the dual-wavelength operation with a single-polarization state at room temperature. The laser output at each wavelength shows an optical signal-to-noise ratio (OSNR) of >60 dB, a side mode suppression ratio (SMSR) of >50 dB, and a polarization extinction ratio of ~35 dB. The proposed EDFL can give stable output under laboratory conditions.

Multiwavelength fiber laser with fine adjustment, based on nonlinear polarization rotation and birefringence fiber filter

We have proposed and demonstrated a multiwavelength fiber laser based on nonlinear polarization rotation (NPR). The mechanism for stable room-temperature multiwavelength operation contributes to the ability of the intensity-dependent loss in NPR to effectively alleviate mode competition. In addition, through tuning the birefringence fiber filter, the lasing wavelength can be accurately tuned in the free spectrum range of the in-line periodic filter.

Two different operation regimes of fiber laser based on nonlinear polarization rotation : passive mode-locking and multiwavelength emission

We have proposed and demonstrated a nonlinear polarization-rotation-based fiber laser with two different operation states: passive mode-locking and multiwavelength emission. The intensity-dependent transmission or loss induced by nonlinear polarization rotation accounts for the distinct operation regimes. Our experiment results indicate that both passively mode-locked pulses and continuous-wave multiwavelength can be generated from the same fiber laser just through adjusting polarizations. Another characteristic of the current multiwavelength laser is that the used periodic filter is a birefringence fiber filter, which facilitates all-fiber integration of the fiber laser, so it is a potential multifunction laser source with all-fiber configuration and convenient manipulation. © 2008 IEEE.

Multiwavelength fiber laser based on nonlinear polarization rotation

Multiwavelength fiber laser is a perfect light source for future wavelength-division-multiplexing optical communication systems. A multiwavelength fiber laser based on nonlinear polarization rotation with up to 18 wavelengths has been proposed and demonstrated. The intensity- and wavelength-dependent loss induced by nonlinear polarization rotation effect is used to alleviate the mode competition in the homogeneous broadening gain medium of erbium-doped fiber. Instead of traditional filters, a polarization-maintaining fiber is inserted into the laser cavity, with which the polarization-dependent isolator composes an equivalent Lyot birefringent fiber filter. The in-line birefringence fiber filter is used to simplify the laser configuration, which benefits systematic integration. The effect of the 980 nm pump power on the multiwavelength generation is investigated. It is shown that the pump power contributes a lot to the evenness of the multiwavelength spectra due to the intensity dependence of nonlinear polarization rotation effect.

Tunable multiwavelength SOA fiber laser with ultra-narrow wavelength spacing based on nonlinear polarization rotation

A tunable multiwavelength fiber laser with ultra-narrow wavelength spacing and large wavelength number using a semiconductor optical amplifier (SOA) has been demonstrated. Intensity-dependent transmission induced by nonlinear polarization rotation in the SOA accounts for stable multiwavelength operation with wavelength spacing less than the homogenous broadening linewidth of the SOA. Stable multiwavelength lasing with wavelength spacing as small as 0.08 nm and wavelength number up to 126 is achieved at room temperature. Moreover, wavelength tuning of 20.2 nm is implemented via polarization tuning.

Multiwavelength fiber laser based on nonlinear polarization rotation

Multiwavelength fiber laser is a perfect light source for future wavelength-division-multiplexing optical communication systems. A multiwavelength fiber laser based on nonlinear polarization rotation with up to 18 wavelengths has been proposed and demonstrated. The intensity- and wavelength-dependent loss induced by nonlinear polarization rotation effect is used to alleviate the mode competition in the homogeneous broadening gain medium of erbium-doped fiber. Instead of traditional filters, a polarization-maintaining fiber is inserted into the laser cavity, with which the polarization-dependent isolator composes an equivalent Lyot birefringent fiber filter. The in-line birefringence fiber filter is used to simplify the laser configuration, which benefits systematic integration. The effect of the 980 nm pump power on the multiwavelength generation is investigated. It is shown that the pump power contributes a lot to the evenness of the multiwavelength spectra due to the intensity dependence of nonlinear polarization rotation effect.

Two different operation regimes of fiber laser based on nonlinear polarization rotation:passive mode-locking and multiwavelength emission

We have proposed and demonstrated a nonlinear polarization-rotation-based fiber laser with two different operation states: passive mode-locking and multiwavelength emission. The intensity-dependent transmission or loss induced by nonlinear polarization rotation accounts for the distinct operation regimes. Our experiment results indicate that both passively mode-locked pulses and continuous-wave multiwavelength can be generated from the same fiber laser just through adjusting polarizations. Another characteristic of the current multiwavelength laser is that the used periodic filter is a birefringence fiber filter, which facilitates all-fiber integration of the fiber laser, so it is a potential multifunction laser source with all-fiber configuration and convenient manipulation. © 2008 IEEE.